TY - JOUR
T1 - Systematic expansion of supercubane cores in manganese oxo clusters with tricarboxylate ligands
AU - Okui, Yayoi
AU - Catusanu, Florina Aurelia
AU - Kubota, Ryoko
AU - Kure, Bunsho
AU - Nakajima, Takayuki
AU - Tanase, Tomoaki
AU - Kajiwara, Takashi
AU - Mikuriya, Masahiro
AU - Miyasaka, Hitoshi
AU - Yamashita, Masahiro
PY - 2011/10
Y1 - 2011/10
N2 - A novel class of high-nuclearity Mn17 and Mn19 mixed-valent complexes, [Mn17(μ-O)12(μ-OMe) 2(μ-kta)6(MeOH)4] (1), [Mn 17(μ-O)14(μ-kta)6L4] [L = bpy (2a), phen (2b), 4,7-Ph2phen (2c), dmf (3)], and [Mn 19(μ-O)14(μ-kta)6(bpy)6]X 3 [X = PF6 (4a), BF4 (4b)], were synthesized by utilizing Kemp's tricarboxylate ligands (H3kta = cis,cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid). The complexes were characterized by X-ray crystallography and reveal mineralomimetic Mn 13 supercubane units, [Mn13(μ-O)14], in which their oxidation states systematically altered, depending on their vertex face-capping ligands and MnII satellite fragments. Complex 2a was converted by treatment with benzoic acid and [Mn2O 2(bpy)4](BF4)3 to a cage-type Mn14 complex, [Mn14(μ-O)12(μ-OH) 6(μ-Hkta)6(bpy)6](BF4) 4 (5), which show ferro-and antiferromagnetic interactions and slow magnetic relaxation at low temperature.
AB - A novel class of high-nuclearity Mn17 and Mn19 mixed-valent complexes, [Mn17(μ-O)12(μ-OMe) 2(μ-kta)6(MeOH)4] (1), [Mn 17(μ-O)14(μ-kta)6L4] [L = bpy (2a), phen (2b), 4,7-Ph2phen (2c), dmf (3)], and [Mn 19(μ-O)14(μ-kta)6(bpy)6]X 3 [X = PF6 (4a), BF4 (4b)], were synthesized by utilizing Kemp's tricarboxylate ligands (H3kta = cis,cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid). The complexes were characterized by X-ray crystallography and reveal mineralomimetic Mn 13 supercubane units, [Mn13(μ-O)14], in which their oxidation states systematically altered, depending on their vertex face-capping ligands and MnII satellite fragments. Complex 2a was converted by treatment with benzoic acid and [Mn2O 2(bpy)4](BF4)3 to a cage-type Mn14 complex, [Mn14(μ-O)12(μ-OH) 6(μ-Hkta)6(bpy)6](BF4) 4 (5), which show ferro-and antiferromagnetic interactions and slow magnetic relaxation at low temperature.
KW - Carboxylate ligands
KW - Cluster compounds
KW - Magnetic properties
KW - Manganese
KW - Mixed-valent compounds
KW - Supercubane cores
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U2 - 10.1002/ejic.201100781
DO - 10.1002/ejic.201100781
M3 - Article
AN - SCOPUS:80053184853
SN - 0365-9496
SP - 4325
EP - 4330
JO - Berichte der deutschen chemischen Gesellschaft
JF - Berichte der deutschen chemischen Gesellschaft
IS - 28
ER -